Phosphites and phosphonates of hydroxyalkyl and hydroxyalkoxyalkyl isocyanurates



United States Patent C) "ice phite, di-p-cresyl phosphite, in an amount of 01-10%, or in the presence of an alkaline catalyst, e.g., an alcoholate or phenolate such as sodium methylate, sodium decylate,

3,121,082 PHOSPHITES AND PHOSPHGNATES OF HY- Z E Y sodium phenolate or potassium cresyiate.

Alvin Guttag, Bethesda, Md., assignoi', by niesne assign- AS ms (hydroxyalkyi) lsocyanurates. there can be ments, to Union Carbide Corporation, a corporation of 5 used (z'hydroxyethyl) lsocyanurate (2'hydroxy' New York propyl) isocyanurate, tris (Z-hydroxybutyl) isocyanurate.

- No Drawing. Filed May 22, 1962,Ser.No. 196,614 Tris y y y isocyanurate can be p p Cl i (Cl, 250-243) in the manner taught by Frazier et al. in the Journal of Organic Chemistry, volume 25, pages l944-1946 (1960). The present invention relates to novel phosphites and 10 Tris (Z-hydroxypropyl) isocyanurate can be formed in the phosphonates. manner described by Frazier (alkylene oxide reacted with It is. an object ofthe present inventionto prepare alcocyanuric acid in the mole ratio of 3: 1 in dimethyl holic hydroxyl containing phosphites which have good formamide with sodium hydroxide catalyst) by replacing temperature stability. 7 the ethylene oxide specifically used in Frazier with propyl- Another object is to prepare phosphites having free ene oxide. Tris (Z-hydroxybutyl) isocyanurate can be hydroxyl groups which can be used to form flame-resistant formed in similar manner by utilizing butylene oxide and polyurethanes. the alkylene oxide.

A further object is to form novel phosphonates. As the triaryl phosphite there can be used triphenyl Still further objects and the entire scope of applicability phosphite, tri p-cresyi phosphite, tri o-cresyl pbosphite, of the present invention will become apparent from the i i xylenyl phosphite,

detailed description given hereinafter; it should be under- T prepare th phosphonates, the isocyanurate phosstood, however, that the detailed description and specific hi are i i d fig by h i i 140 mole examples, while indicating preferred embodiments of the ent f n alkyl halide, e.g., butyl bromide, arnyl bromide invention, are given by 'Wayof illustration only, since varior l h1 id 0115 Changes and modifications Within the Spirit and pe Examples of compounds within the presentinvention are of the invention will become apparent to those skilled in trig t i (Lhydroxyethyl) isocyanurate] phosphite, his

the art from this detailed description [tris (Z-hydroxypropyl) isocyanurate] phosphite, tris [tris It has now been found that these objects can be atz d b l) isocyanumte] h hit bi [t -i (2- taiiied'by forming the iris (tiishydmxyaikyi) isocyanuiaie hydroxyethyl) isocyanurate] bis (Z-hydroxyethyl) ethyl PhOSPhiiES having the following formula isocyanurate phosphonate, bis [tris (Z-hydroxypropyl) iso- NRO- P cyanurate] bis (2-hydroxypropyl) Z-methy-lethyl isocya- 1 nurate phosphonate, bis [tris (Z-hydroxybutyl) isocyal' l Y C /NROH J phosphonate.

nurate] bis(2 hydroxybutyl) 2 ethylethyl isocyanurate Unless otherwise indicated, all parts and percentages are where R is an alkylene group having 2 to 4 carbon atoms, Example 1 by weight.

e.g., ethylene, propylene, :l-ethyl ethylene, or an alkylene 3 moles (783.7 grams) of finely divided tris (2-hydroxy oxyalkylene or an alkylene polyoxyalkylene group. The 40 ethyl) isocyanurate, 1 mole of triphenyl phosphite and 3 phosphonates of the present invention are formed by grams of diphenyl phosphite Were heated in a vacuum, Arbuzov rearrangement of the corresponding phosphites. about 15 mm, and the phenol formed removed by distil- The phosphiteand phosphonate compounds of the preslation. The viscous liquid residue in the pot was tris e'nt invention are useful as reactants in forming fiaine- [tris (Z-hydroxyethyl) isocyanurate] phosphite. resistant polyesters and polyurethanes. Thus, they can '45 V be reacted with a slight excess of an organic isocyanatle, e. toluene diisoc anate, on an e uivalence basis in t e j pr esence of a srnziil amount of in ater to produce polyone H1016 0f iris [tris y 'g y iy lsocyaiiui'atel urethane foams having good flame and fire resistance. Phosphlie was hejaied to -1130 Wlih Percent Such foams are useful as building insulation, upholstery 50. y bmmide for 5 hfiilfs to form bis U filling, etc. The phosphites of the present invention also droxy y isocyamllfliel (2-hydroxyethyl) etnyl -are useful as stabilizens for halogen containing resins. Cyamlrate phosphonate as a viscous liquid having the for- Exzimple 2 The phosphites and phosphonates are also useful as cross mula i H /CVNCHQOHQOH N-cmonio P-CH2OH2-N 0'=o 0 \G fiN-oHioHi0-H linking and stabilizing agents for epoxy reiing, e .g., from Example 3 -"e s Well as'bis henol A e ic lor rin. alfo phites of the present in i/ention are prepared Procedure of f P 1 Was reheated pl by reacting 3 moles of a tris (hydroxyalkyl) isocyanurate 7 m5 y y y lsoeyamll'filie Wlth 3 m es f ms with one mole of a triaryl phosphite in the presence of a 0 Y YP 'QPY isocyamll'aie recover lifls (E ycatalyst such asa diarylphosphite or a dialkyl phosphite, I droxypropyl) isocyanurate] phosphite as a viscous liquid e.g., diphenyl phosphite, diethyl phosphite, didecyl phosresidue after removal of the phenol formed by distillation.

Example 4 One mole of tris [tris (Z-hydroxypropyl) isocyanurate] phosphite was heated to 125 C. with 5 mole percent of n-butyl bromide for 6 hours to form [tris (Z-hydroxypropyl) isocyanurate] phosphonate as a viscous liquid having the formula While most of the product formed will have the formula indicated above, there will be a minor fraction having primary hydroxyl groups since the starting tris (2- hydroxypropyl) isocyanurate is admixed with a minor amount of isomeric material wherein the hydroxyl group is primary due to the method of manufacture of the starting isocyanurate.

Additionally, according to the invention there can be prepared tris [tris (2-hydroxyalkyloxyalkyl) isocyanurate] phosphites and the isomeric phosphonates and tris [tris (Z-hydroxyalkylpolyoxyalkyl) isocyanurate] phosphites and the isomeric phosphonates. The isomeric phosphonates are prepared from the phosphites in the manner previously described. These phosphites and phosphonates can be used in the manner previously set forth.

Examples of such phosphites and phosphonates are tris [tris (Z-hydroxyethoxyethyl)isocyanurate] phosphite and the isomeric phosphonate, tris [tris (2-hydroxypolyethoxyethyl) isocyanurate] phosphite wherein the polyethoxy group has a molecular weight of 2000 and the isomeric phosphonate, tris [tris (2-hydroxypropoxypropyl) isocyanurate] phosphite and the isomeric phosphonate, tris [tris (Z-hydroxypolypropoxypropyl) isocyanurate] phosphite wherein the polypropoxy group has a molecular weight of 3000 and the isomeric phosphonate, tris [tris (2-hydroxypropoxypolyethoxy polypropoxypropyl) isocyanurate] phosphite wherein the polyethoxy portion of the molecule has a molecular weight of 400 and the polypropoxy portion of the molecule has a molecular weight of 1900, tris [tris (Z-hydroxybutoxybutyl) isocyanurate] phosphite and the isomeric phosphonate.

These products man be prepared by substituting for the 3 moles of tris (2-hydroxyalkyl) isocyanurate employed for reaction with the triphenyl phosphite or the like 3 moles of tris (2-hydroxyalkoxyalkyl) isocyanurate or 3 moles of tris (Z-hydroxypolyalkoxyalkyl) isocyanurate. Examples of such starting materials include tris (2-hydroxyethoxyethyl) isocyanurate, tris (Z-hydroxypropoxypropyl) isocyanurate, tris (Z-hydroxybutoxybutyl) isocyanurate, tris (2-hydroxypolyethoxyethyl) isocyanurate where the polyethoxy group has a molecular weight of 2000, tris (Z-hydroxydipropoxypropyl) isocyanurate, tris (2-hydroxypolypropoxypropyl) isocyanurate, where the polypropoxy group has a molecular weight of 3000, tris (Z-hydroxypropoxypolyethoxypolypropoxypropyl) isocyanurate wherein the polyethoxy portion of the molecule has a molecular Weight of 400 and the polypropoxy portion of the molecule has a molecular weight of 1900.

The tris (2-hydroxyalkoxyalkyl) isocyanurates and tris (Z-hydroxypolyalkoxyalkyl) isocyanurates can be prepared in several ways. Thus, they are sometimes formed as impurities when reacting an alkylene oxide such as ethylene oxide or propylene oxide with cyanuric acid in the manner described in the Frazier et al. article. Alternatively, they can be prepared by reacting tris (2- hydroxyethyl) isocyanurate, or tris (Z-hydroxypropyl) isocyanurate, or tris (Z-hydroxybutyl) isocyanurate with the required amount of ethylene oxide, propylene oxide or 1,2-butylene oxide or mixtures thereof with an alkaline moles of propylene oxide with one mole of tris (2-hydroxypropyl) isocyanurate.

Example 5 The procedure of Example 1 was repeated replacing the tris (2-hydroxyethyl) isocyanurate with 3 moles of tris (Z-hydroxyethoxyethyl) isocyanurate to form tris [tris (2- hydroxyethoxyethyl) isocyanurate] phosphite as a viscous liquid residue after removal of the phenol by distillation. By the addition of 5 mole percent of n-butyl bromide to the product and heating to 130 C. for 5 hours there was formed the isomeric phosphonate.

Example 6 The procedure of Example 1 was repeated replacing the tris (Z-hydroxyethyl) isocyanurate with 3 moles of tris (2-hydroxypropoxypropyl) isocyanurate to form tris [tris (Z-hydroxypropoxypropyl) isocyanurate] phosphite as a viscous liquid residue after removal of the phenol. The product was converted to the isomeric phosphonate by heating for 7 hours with 4 mole percent of n-butyl bromide.

Example 7 The procedure of Example 1 was repeated replacing the tris (2-hydroxyethyl) isocyanurate with 3 moles of tris (2-hydroxypolyethoxyethyl) isocyanurate wherein the polyethoxy group has a molecular weight of 2000. The product was a viscous liquid. This was converted to the isomeric phosphonate by heating for 6 hours with 5 mol percent of n-butyl bromide.

I claim:

1. A member of the group consisting of N-RO- P and alkyl) alkylisocyanurate phosphonate wherein there are 2 to 4 carbon atoms in each hydroxyalkyl group and in the alkyl group, said compound having the formula:

8. Tris [tris(hydroxyalkoxyalkyDisocyanurate]phosphite wherein there are 2 to 4 carbon atoms in the alkyl group and in the alkoxy group.

9. Tris tris(hydroxypolyalkoxyalkyl)isocy anurate]phos- 0 N R O I R 5 phite wherein there are 2 to 4 carbon atoms in each alkoxy Q T PT I group and in the alkyl group. 0:0 0:0 /N\ 10. A phosphonate having the formula: HORN N-ROH 0:0 0:0

\ l I II 0 HORN NROH N-RORO- P-ROR ll 10 0 2 0 0:0 0:0 N

II I 0 HOROR-N N-ROROH 0:0 0:0 where R is alkylene having 2 to 4 carbon atoms, 0 HOROR-N N-ROROH 6. Bis[tris(2-hydroxyethy1)isocyanurate]bis (2 hyg 2 C droxyethyl)ethylisocyanurate phosphonate, said compound 15 having the formula:

wherein each R is alkylene having 2 to 4 carbon atoms.

H N-CHzCl-IzO- P-CHzfiJHi 0:0 0:0 N

l l H0 O1i-I2CIhN\ /NCH2CH1OH 0:0 (3:0

(if HOCH2CH2N NCIHQCHZOH o 2 7 E 0 7. Bis[tris(Z-hydroxypropyl)isocyanurate]bis (2 hydroxypropyl) 2-methy1ethy1isocyanurate phosphonate, said compound having the formula:

NOHOHO- P-OHCH:

HOCHCHgN\ /NCH2CHOH 0:0 1:0

CH3 (If CH: IIO(I}HOH2N\ /N HzCHOH 0 2 0H: C 0H:

References Cited in the file of this patent UNITED STATES PATENTS Frazier et 1946 (1960).

OTHER REFERENCES a1.: J. Org. Chem, vol. 25, pages 1944 to 

1. A MEMBER OF THE GROUP CONSISTING OF 